Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low‐Spin Cobalt(III) Phosphanido Complex

Coburger, Peter; Demeshko, Serhiy; Rödl, Christian; Hey‐Hawkins, Evamarie; Wolf, Robert

doi:10.1002/anie.201709140

Cited by 32 publications

(23 citation statements)

References 66 publications

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“…Furthermore, these reactions may result in unusual compounds. Thus, the homoleptic cobalt(III) phosphanido complex [K(thf) 4 ][Co{1,2‐(P t Bu) 2 C 2 B 10 H 10 } 2 ], prepared by an unprecedented oxidative addition of the P–P bond of an ortho ‐carborane‐substituted 1,2‐diphosphetane to cobalt(–1) has been reported and oxidative addition of a P–P bond in cyclo ‐(P 5 Et 5 ) to rhodium(I) resulted in the metallacyclic complex [(NacNac)RhP 5 Et 5 ] {NacNac = HC[CMeN(2‐6 i Pr 2 C 6 H 3 )] 2 } …”

Section: Introductionmentioning

confidence: 99%

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

2019

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The reaction of [M(CO) 4 L x ] {M = Cr, W, L = MeCN, x = 2; M = Mo, L = 2,5-norbornadiene (nbd), x = 1} with cyclo-(P 5 Ph 5 ) led to an unusual transformation reaction including the oxidative addition of a P-P bond to the Group 6 metal carbonyl, the insertion of MeCN into a P-P bond, and the formation of an M-M bond. The products were characterized by IR and 31 P{ 1 H} NMR spectroscopy, ESI mass spectrometry and single

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Section: Introductionmentioning

confidence: 99%

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

2019

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“…In these cases, phosphorus atom is connected only to one metal center and can exhibit either pyramidal geometry with one lone pair or planar geometry with the lone pair participating in π bonding , . It should be noted that, among the high number of bridged phosphido complexes,, there are many reports of transition metal complexes featuring non‐bridging, terminal phosphido ligands,, including some supported by nacnac ligands . However, only a handful of known terminal phosphido complexes, incorporate iron and, in most cases, these complexes are supported by carbonyl or cyclopentadienyl co‐ligands.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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We report the synthesis of the first series of terminal phosphido iron complexes supported by a -diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono-or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl 2 Li(dme) 2 ] with the R 2 PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and the bulkiness of the substituents at the P-atom. The structures of the synthesized compounds were determined by single-crystal X-ray diffraction, which revealed that the iron [a] Reports by Webster et al. [14,27,43,[98][99][100][101][102] on the use of an iron(II) -diketiminato pre-catalyst, [(Dippnacnac)Fe(CH 2 TMS)] for the hydrophosphination of unsaturated hydrocarbons and dehydrocoupling of primary and secondary phosphines postulated the formation of an intermediate terminal phosphido complex. In the case of hydrophosphination, the authors proposed that the active catalyst is a monomeric phosphido complex; however, the active species was isolated as a bridging complex, [(Dippnacnac)Fe(PRH(CH 2 ) 3 CH=CH 2 )] 2 . [27] Worth emphasizing is that this compound is not only the first -diketiminate iron complex bridged by phosphido groups, but also a perfect example highlighting the catalytic potential of lowcoordinate iron compounds. The hydrophosphination and dehydrocoupling processes are both ideally suited for the synthesis of novel P-containing compounds and their catalytic improvements will expand the access to functionalized phosphines, diphosphanes, and other P-containing derivatives.Recently, we have reported a new synthetic method to access iron(II) phosphanylphosphido complexes using as starting materials the -diketiminato complex [(Dippnacnac)FeCl 2 -Li(dme) 2 ] [103] and lithium salts of diphosphanes, R 2 P-P(SiMe 3 )Li (R = iPr, tBu). [104] Due to the propensity of the diphosphorus ligand to undergo P-P bond cleavage, these iron(II) phosphanylphosphido complexes have rather limited catalytic potential. Considering this limitation, we directed our attention to iron(II) complexes with phosphido R 2 P ligands. In this paper, we detail the syntheses, structures, and spectroscopic characterization of the first series of terminal phosphido Fe II complexes stabilized by -diketiminates. We also discuss their thermal stability and catalytic activity in promoting the dehydrocoupling of secondary phosphines. Reaction of [(Dippnacnac)FeCl 2 ] with Ph 2 PLi:To the suspension of [(Dippnacnac)FeCl 2 ] (0.272 g, 0.5 mmol) in 2.5 mL of solvent (tolu-Eur.

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“…We have developed the chemistry of the carborane‐substituted 1,2‐diphosphetane 1 (Scheme ) –. We reasoned that the release of ring strain in this compound might present a similar driving force for the insertion of selenium in the P−P bond as in bulky diphosphanes.…”

Section: Introductionmentioning

confidence: 99%

Exploiting the Ring Strain of Diphosphetanes: A Synthetic and Computational Approach towards 1,2,5‐Selenadiphospholanes

et al. 2018

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A carboranyl‐based meso‐1,2,5‐selenadiphospholane diselenide was synthesised starting from a strained carborane‐substituted 1,2‐diphosphetane and subsequently reduced to an unprecedented carboranyl‐based meso‐1,2,5‐selenadiphospholane. The electronic structure and the bonding situation for both compounds were investigated by density functional theory (DFT), Natural Bond Orbital (NBO) analyses, Fractional Occupation Density (FOD) analysis, Complete Active Space Self Consistent Field (CASSCF) calculations and time‐dependent DFT (TDDFT) calculations. Ring‐opening reactions of meso‐1,2,5‐selenadiphospholane with nucleophiles and electrophiles are reported together with calculated reaction mechanisms (DFT level). Isolated compounds were characterised by NMR and IR spectroscopy, high‐resolution mass spectrometry, elemental analysis and single‐crystal X‐ray diffraction.

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Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low‐Spin Cobalt(III) Phosphanido Complex

Cited by 32 publications

References 66 publications

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

Exploiting the Ring Strain of Diphosphetanes: A Synthetic and Computational Approach towards 1,2,5‐Selenadiphospholanes

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Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low‐Spin Cobalt(III) Phosphanido Complex

Cited by 32 publications

References 66 publications

Unusual Reactivity of cyclo‐(P5Ph5): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Unusual Reactivity of cyclo‐(P5Ph5): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

Exploiting the Ring Strain of Diphosphetanes: A Synthetic and Computational Approach towards 1,2,5‐Selenadiphospholanes

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Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond

Unusual Reactivity of cyclo‐(P₅Ph₅): Oxidative Addition at a Group 6 Metal Carbonyl and Insertion of Acetonitrile into a P–P Bond